Metalliferous nitro-azo-dyestuffs



Patented July 12, 1938 METALLIFEROUS NITRO-AZO-DYESTUFFS Hans Schindhelm, Frankfort-on-the-Main-Fechenheim, Germany, assignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application November 2, 1935, Se-

rial No. 48,057. In Germany November 6,

1 Claim.

This invention relates to new metalliferous nitro-azo-dyestufis, more particularly to copper compounds of dyestuffs corresponding to the general formula:

wherein R means the radical of a diazotization a component of one of the groups consisting of compounds of the benzene and naphthalene series, X-stands for one of the groups consisting of hydrogen and a sulfonic acid group and Y stands for one of the group consisting of an acyl radical and a radical of the benzene series.

These dyestuffs are obtainable by diazotizing a nitro-diazo compound, combiningit with a l-amino 2 naphthol ether, diazotizing again, combining with an N-derivative of 2-amino-5- 2 hydroxy-naphthalene-7-sulfonic acid and finally S 0311 V 0-02115 NH-CO om-O-n: N=N

I SOaH treating the dyestufi with agents delivering cop- The paste is then dissolved in Water and the per.

As first components may be used for instance: nitranilines, nitrotoluidines, nitro anisidines, nitro-chloroanilines, nitr'aniline-sulfonic acid, nitro naphthylamine-sulfonic-acids, nitrophenyl-azo-amino-naphthalene sulfonic acids.

As middle components may be used: the alkyl ethers of 1-amino-2-hydroxy-naphthalene or their sulfonic acids.

As third component may be used for instance: 2-acetylamino-, 2-benzoylamino-, 2-phenylamino-, 1,2 imidazolyl 5 hydroxy-naphthalene-7- sulfonic acids.

The new metalliferous nitro-azo-dyestufis dye.

Example 1 13.8 parts of p-nitraniline are diazotized in the ususal manner with 35 parts of hydrochloric acid (d=1.15) and 6.9 parts of sodium nitrite. The diazo solution is then allowed to flow at 0 into a solution of 28.9 parts of the sodium salt of l-amino--2-ethoxynaphthalene 6 sulfonic acid mixed with a solution of sodium acetate. the mass is heated to' and rendered alkaline 1 by the addition of sodium carbonate.

Then

The precipitated dyestuff isisolated by filtration and freed from the adhering mother lye by washing it with salt water.

Then the paste is dissolved in 2000 liters of water and again diazotized by means of 7 parts of sodium nitrite and 35 parts of hydrochloric acid (d=1.15).

When the diazsolution is heated to boiling, while stirring, for some hours with 35, parts of crystallized copper sulfate in presence of acetic acid. Thereafter the product is isolated by filtration, washed with water, then made to a paste with sodium carbonate and water and again isolated therefrom.

The new dyestuff represents when dry a dark powder soluble in water with a greenish-grey, and in concentrated sulfuric acid with a green color, and dyes cotton greenish-grey shades of an excellent fastness to light.

Example 2 A diazo compound prepared in the same manner from 13.8 parts of m-nitraniline is allowed to run into a solution of 28.9 parts of the sodium 'salt of l-amino-2-ethoxynaphthalene-6-sulfonic acid, mixed with a solution of sodium acetate. The combination to the amino-azo-dyestufi' is instantly finished. The mass is filtered and the filtrate is washed with a little quantity of water. The paste is then mixed 'with .ice and transformed intothe diazo-azo-compound by means of 35 parts of hydrochloric acid and 6.9 parts of sodium nitrite.

The reaction product is poured hering excess of copper sulfate.

into a solution of 40 parts of the sodium salt of 2 m carboxyphenylamino 5 naphthol 7 OIN sulfonic acid mixed with pyridine. The dyestufi precipitated by the addition of common salt is isolated by filtration and washed. It corresponds to the formula:

o-ozm sonar S 0311 Thereafter the dyestufi paste is dissolved in water and transformed into the cupriferous compound by heating it for some hours to boiling. under a refiux condenser, while stirring in anacetic acid medium with 35. parts of crystallized copper sulfate. with cold water and thereby freed from the ad- Then the paste is mixed with a diluted soda lye and dried.

The dyestuif represents a black powder, which dissolves in Water with a greenish-grey, in concentrated sulfuric acid with a green color and dyes cotton greenish-grey shades of anextraordinary fastness to light.

Example 3' H 29 parts; of the sodium salt of 6.-nitroe2-amino-' naphthalene-B-sulfonic acid are diazotized with 35 partsof hydrochloric acid and 6.9 parts of the OCH sodium salt of nitrous acid. This diazo compoundis combined inthe usual manner, while stirring, with an aqueous solution of 28 parts of the sodium salt of l-amino-2-ethoxy-naphthalene-fiesulfonic acid. After some minutes the copulation, is finished and the. formed dyestufi is isolated by filtration. v

Then the aminoazo-dyestufiis diazotized with 6.9 parts of sodium nitrite and 35 parts of hydrochloric acid (d=1.15).. The. excess of hydrochloric acid isneutralized by the addition of sodium acetate and the diazo. compound is coupled with a solution of 36 parts of the sodium salt of 2ebenzoylamino-5-naphthol- 7-s u 1 Toni 0 acid.

When the copulation is, finished-,.the dyestufi is precipitated by the addition-of common-salt. The massis filteredand-the filtrateis--washed,. dissolved in water and acidified by meanszof- N=N N=N The mass is filtered, the filtrate washed acetic acid. The dyestufi corresponds to the formula: p

S OaH 0-G1H5 NHC 0O SO3H After the addition of a solution of 35 parts of crystallized. copper sulfate the reaction product is boiled for some hours, while stirring under a reflux condenser. Then the dyestuff is isolated OOH- by filtration, washed, made to a paste with sodium carbonate and dried. The dark powder thus obtained dissolves in waterwith a greenishgrey, in concentrated sulfuric acid with a green color and dyes cotton greenish-grey shades of an excellent fastness to light.

Emample 4 16.8 parts of 5-nitro-2-amino-anisole are mixed with 36 parts of hydrochloric acid (d=1.15) ,luntil the whole base is transformed-into the chloro-- hydrate, and the paste is 'diazotized with 6.9. parts of sodium nitrite. Thdudiazo-solution is coupled as describedin Example 1 with the sodium salt of 1amino-2-ethoxy-naphthalene-6- sulfonic acid, and the intermediate compound is isolated. The dyestufi' is further diazotized with 35 parts of concentratedv hydrochloric acid and 7 partsof sodium nitrite and coupled witlra solution of the sodium salt of Z-(m-carboxyphenylamino) -5-naph'thol-7-sulfonic acid" containing pyridine. The dyestufi, corresponding to the formula:

SOaH Hols NHQ N=N COOH is isolated inthe usual manner and mixed with. After the addition ofaceti'c acidanda' solution of 35.parts of. crystallized copper sulfate water.

in a little quantity'of Water, thejmixture is .boiled forsome hours while stirring underv a refluxcom denser. Then the dyestufl is isolated by' filtrae tion, washed and dried: The .blackpowder" dis-.

solves in water to a blue,'in concentratedsulfuric' acid to a greyish-bluesolution and dyes cotton grey shades of an excellent fastness to light.

I claim:

of the dyestufl corre- The copper compound sponding to the formula:.

SOaH

which compound represents a blacks-powder SO19"; uble-in. water to a blue, in concentrated sulfuric acid to a-greyish blue'solution, dyeing cotton grey" shades of an excellentfastness to light HANS SCHINDI-IEIM;

" con 

